Oil-soluble n-long chained acyl acidic amino acid ester, mixture thereof and perfuming cosmetics containing the same

ABSTRACT

Herein are disclosed (1) an oil-soluble N-long chained acyl acidic amino acid mono- or di-ester having at least one sterol ester in the molecule, which is a novel compound of excellent emulsifying and hydrating performances, (2) an oily composition consisting of or comprising a mixture of such esters, and (3) perfuming cosmetics blended with such ester or such oily composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention concerns an oil-soluble N-long chained acyl acidicamino acid ester having at least one sterol ester, an oily compositionconsisting of or comprising a mixture of such esters, as well asperfuming cosmetics prepared by blending such ester or such oilycomposition.

2. Description of the Prior Art

Various kinds of esters have generally been used as oleo-phase materialsfor skin and hair cosmetics and medicines for external application.Further, amino acid type surface active agents of natural origin andwith high safety have often been used recently. By the way, most of suchamino acid type surface active agents are hydrophilic and, asoil-soluble amino acid type surface active agent usable as theoleo-phase material for perfuming cosmetics, etc., N-lower acyl acidicamino acid diesters, N-long chained acyl acidic amino acid diesters,N-long chained acyl neutral amino acid ester and N,N-dilong chained acylbasic amino acid esters and the like have been known.

However, although the known compounds as described above have somedegree of emulsifying and hydrating performances, both of theperformances are remarkably low in the N-long chained acyl acidic aminoacid higher alcohol diesters, and more excellent high performances arerequired for the improvement of the performance, for example, ofperfuming cosmetics.

On the other hand, various kinds of sterol esters have hitherto beenused as the oleo-phase material having the excellent emulsifyingperformance and further of excellent moisture permeability because ofits melting point of 35°˜40° C. near the body temperature. Excellentmoisture permeability prevents the skin blocking caused by cosmetics.They have particularly preferred hydrating performance but involve adrawback that the use of products gives somewhat heavy feeling when theyare blended with perfuming cosmetics.

OBJECT AND SUMMARY OF THE INVENTION

An object of the present invention is to provide an oil-soluble N-longchained acyl acidic amino acid mono- or di-ester having at least onesterol ester in the molecule, which is a novel compound of excellentemulsifying and hydrating performances.

Another object of the present invention is to provide an oilycomposition consisting of or comprising a mixture of such esters.

A further object of the present invention is to provide perfumingcosmetics blended with such ester or such oily composition as describedabove.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Referring more specifically, the first aspect of the present inventionresides in an N-long chained acyl acidic amino acid mono- or di-ester,which is oil-soluble and represented by the following general formula(I): ##STR1## in which each of X and Y, which may be identical with ordifferent from each other, represents an ester forming residue of asterol, or one of X and Y represents an ester forming residue of asterol and the other of them represents H or an ester forming residue ofa liquid higher alkyl or alkenyl mono-hydric alcohol with 8 to 30 carbonatoms or an ester forming residue of a solid higher alkyl mono-hydricalcohol with 12 to 38 carbon atoms, COR represents a long chained acylgroup with 8 to 22 carbon atoms and n is 1 or 2.

The N-long chained acyl acidic amino acid moiety of the ester accordingto the present invention represented by the general formula (I) is anN-long chained acyl aspartic acid (n=1 in the formula (I)) or N-longchained acyl glutamic acid (n=2 in the formula (I)), in which the longchained acyl group may be an acyl group derived from a saturated orunsaturated fatty acid with 8 to 22 carbon atoms, for example, an acylgroup of a fatty acid of a single ingredient such as lauric acid,palmitic acid, stearic acid and oleic acid, as well as an acyl group ofmixed fatty acids obtained from natural products such as palm oil fattyacid, tallow fatty acid and hardened tallow fatty acid and an acyl groupof synthetic fatty acids (including branched fatty acids). Such longchained acyl groups are adopted for the acyl group with an aim ofproviding a hydrophobic property. The acidic amino acid moiety may be ofan optically active form or a racemic form.

As the sterol, there can be mentioned, for example, cholesterol,phytosterol and hydrogenation product thereof (which may be of animal orvegetable origin). As the liquid higher alkyl or alkenyl alcohol with 8to 30 carbon atoms, there can be exemplified a natural or syntheticaliphatic alcohol with 8 to 30 carbon atoms, which is liquid at normaltemperature, for example, branched alcohol such as 2-octyl dodecylalcohol and, in addition, unsaturated alcohol such as oleyl alcohol.Then, as the solid higher alkyl alcohol with 12 to 38 carbon atoms,there can be mentioned a saturated monohydric alcohol with 12 to 38carbon atoms, which is solid at normal temperature, for example, cetylalcohol and behenyl alcohol.

The ester represented by the general formula (I) of the presentinvention can be prepared by reacting an N-long chained acyl acidicamino acid and a sterol and, if necessary, a liquid higher alkyl oralkenyl mono-hydric alcohol with 8 to 30 carbon atoms or a solid alkylmonohydric alcohol with 12 to 38 carbon atoms by a generally knownesterifying method, for example, (1) condensating dehydration by heating(under normal or reduced pressure), (2) ester-exchanging reaction, (3)condensating dehydration under azeotropic boiling or the like. Inparticular, preparation by condensation dehydration under azeotropicboiling is optimum in view of reaction conditions, and yield and purityof the products.

Referring more specifically, for the sterol di-ester in which both of Xand Y are the ester forming residues of sterol, 20˜22 mols of sterolbased on one mol of the N-long chained acyl acidic amino acid and 10 to50% of a non-polar solvent such as benzene or toluene (% by volume basedon the charged amount of the N-long chained acyl acidic amino acid andthe alcohol) are charged and sufficiently stirred and mixed in areaction vessel and, subsequently, 0.01 to 1.5 mol of an acidic catalystsuch as sulfuric acid, o-toluene sulfonic acid, hydrogen chloride orstrongly acidic ion exchange resin is added and stirred under heating at70° to 200° C. for 1 to 10 hours. In this case, the reaction is promotedby removing the water by-produced during the reaction as much aspossible.

For the sterol mono-ester in which only one of X and Y is an esterforming residue of a sterol, while the other of them is H, thepreparation method is similar to that for the sterol di-ester except forreducing the amount of the sterol used to one-half relative to theN-long chained acyl acidic amino acid. Preparation is of course notrestricted only to the above-mentioned method but any of methods may beused so long as the N-long chained acyl acidic amino acid mono- ordi-ester is finally derived, for example, a method of reacting an acidicamino acid at first with a sterol in the presence of an acidic catalystinto the corresponding acidic amino acid mono- or di-ester, which isthen acylated into an N-long chained acyl form by a so-called SchottenBauman reaction in which the mono- or di-ester is reacted with a longchained fatty acid halide in the presence of a basic catalyst.

For the mixed ester in which one of X and Y is an ester forming residueof a sterol and the other of them is an ester forming residue of aliquid or solid higher mono-hydric alcohol, an N-long chained acylacidic amino acid, 2.0 to 2.2 mol of a sterol-containing mixed alcohol(the sterol and the higher mono-hydric alcohol may be in an equi-molarmixing ratio) based on one mol of the N-long chained acyl acidic aminoacid and 10 to 50% of a solvent such as benzene or toluene (% by volumebased on the charged amount of the N-long chained acyl acidic amino acidand the alcohol) are charged in a reaction vessel and mixed understirring sufficiently and, subsequently, 0.01 to 1.5 mol of an acidiccatalyst is added and stirred under heating at 70°to 200° C. for 1 to 10hours. In this case, the reaction is promoted by removing the waterby-produced during the reaction as much as possible. Preparation methodis of course not restricted only to the above-mentioned method but anyof methods may be used so long as the N-long chained acyl acidic aminoacid mixed di-ester is finally derived, for example, a method ofreacting at first an acidic amino acid with the sterol-containing mixedalcohol as described above in the presence of an acidic catalyst intothe corresponding acidic amino mixed di-ester, which is then acylatedinto an N-long chained acyl form by a so-called Schotten Bauman reactionin which the mixed diester is reacted with a long chained fatty acidhalide in the presence of a basic catalyst.

The aimed-at ester can be isolated from the ester reaction mixture by acustomary method such as column chromatography.

An N-long chained acyl acidic amino acid ester or a mixture thereofaccording to the present invention represented by the general formula(I) synthesized by the method described above may be modified variouslyin accordance with the purpose of use, that is, those having liquid tosolid nature and those having low to high viscosity depending on thedifference of the acyl group, or depending on the composition in a caseof using a sterol-containing alcohol mixture as the alcohol.

The N-long chained acyl acidic amino acid ester according to the presentinvention has a feature capable of improving the emulsifying performanceand the hydrating performance, which are insufficient in conventionalhigher alcohol di-ester of N-long chained acyl acidic amino acid, byintroducing a sterol into the ester portion, improving viscous and heavyfeeling in the conventional sterol ester and providing affinity andemollient property to skin and hair. The ester is also capable of givingperfuming cosmetics excellent moisture permeability when incorporatedtherein.

The hydrating property of the oil-soluble N-long chained acyl acidicamino acid ester according to the present invention is shown in Table 1.As apparent from Table 1, the ester mixtures according to the presentinvention (specimens Nos. 1˜15. The specimens Nos. 1˜15 are the same asspecimens Nos. 1˜15 in Table 2, respectively.) have more excellenthydrating power, form firm W/O type emulsion and, accordingly, havestrong emulsifying power as compared with existent N-long chained acylacidic amino acid higher alcohol diester and polyoxyalkylene higheralcohol ether di-ester of N-long chained acyl acidic amino acid. Liquidparaffin and vaseline which have originally no hydrating power showexcellent hydrating power when blended with a small amount of an esterof the present invention, i.e., the ester can improve hydrating power ofliquid paraffin and vaseline.

The excellent moisture permeability of the oil-soluble N-long chainedacyl acidic amino acid ester according to the present invention is shownin Table 1a. It can be seen from the table that perfuming cosmeticscomprising an ester of the present invention do not prevent normal skinmetabolism such as unperceivable sweating and skin breathing, and thatvaseline which is originally poor in moisture permeability is improvedin that property when blended with an ester of the present invention.

                  TABLE 1                                                         ______________________________________                                        Hydrating property of amino acid type sterol ester                                   Hydrating                   Hydrating                                         property                    property                                   Specimen                                                                             (%)*      Specimen          (%)*                                       ______________________________________                                        No. 1  429.3     No. 11            453.4                                      No. 2  365.2     No. 12            752.3                                      No. 3  510.4     No. 13            853.1                                      No. 4  523.5     No. 14            440.2                                      No. 5  599.0     No. 15            873.6                                      No. 6  514.9     A 1:9 mixture of Spec. No. 3                                                                    500                                                         and liquid paraffin                                          No. 7  624.4     A 1:9 mixture of Spec. No. 3                                                                    430                                                         and vaseline                                                 No. 8  474.7     N-lauroyl glutamic acid                                                                          88.4                                                       di-2-octyldodecyl ether                                      No. 9  419.6     N-lauroyl glutamic acid                                                                         123.1                                                       di-POE(2 mol)-octyldodecyl                                                    ether                                                         No. 10                                                                              443.8     N-lauroyl glutamic acid                                                                         129.0                                                       di-POE(5 mol)-octyldodecyl                                                    ether                                                                         N-lauroyl glutamic acid                                                                         183.2                                                       di-POE(2 mol)-stearyl ether                                                   N-lauroyl glutamic acid                                                                         189.6                                                       di-POE(5 mol)-stearyl ether                                  ______________________________________                                         *100 g of specimen is sufficiently stirred under gradual addition of ion      exchanged water to form a W/O type emulsion and the hydrating power is        defined as a maximum amount of water added that can be emulsified into th     W/O type emulsion.                                                       

                  TABLE 1a                                                        ______________________________________                                        Moisture permeability                                                         Specimen       Moisture permeability (%)**                                    ______________________________________                                        No. 3          13.0                                                           Lanolin        5.5                                                            Vaseline       1.3                                                            a 1:1 mixture of Spec.                                                                       6.3                                                            No. 3 and vaseline                                                            ______________________________________                                         **A specimen is spread in an amount of 0.9 mg/cm.sup.2 on a circular shee     (7 cm in diameter) of cellophane and the cellophane sheet is put on a         moisture permeable cup (JIS Z0208). The cup is let stand under an             atmosphere of R.H. 90% at 25° C. for 24 hours. The moisture            permeability is determined on the weight change in the water content, and     however, standardized by comparing with the case of an unspread cellophan     sheet similarly processed as control, its moisture permeability being         100%.                                                                    

Now, the present inventors have made an earnest study, taking notice onthe emulsifying and hydrating performance of the sterol estersrepresented by the general formula (I), developed an amino acid typeoleo-phase material having excellent emulsifying and hydratingperformances and free from heavy feeling of use which is the drawback ofthe sterol ester and has accomplished the present invention in thesecond to the fourth aspects.

The second aspect of the present invention concerns an oily sterolcomposition comprising an oil-soluble N-long chained acyl acidic aminoacid mono- and/or di-ester (group C ester) represented by the generalformula (I), and at least 5 mol% of an oil-soluble N-long chained acylacidic amino acid di-ester (group Ca ester) represented by the followinggeneral formula (Ia): ##STR2## where one of Xa and Ya represents anester forming residue of a sterol, the other of them represents an esterforming residue of a liquid higher alkyl or alkenyl mono-hydric alcoholwith 8 to 30 carbon atoms, and COR and n have respectively the samemeanings as those in the general formula (I) described above.

Such an oily ester composition can be obtained, for example, by thefollowing procedure. That is, an ester belonging to the group Ca esteris prepared by a preparation method for the group C ester, to which anester belonging to the group C ester but not belonging to the group Caester is added at such a ratio that the former is contained at least by5 mol%.

The third aspect of the present invention concerns an oily compositioncomprising:

(1) an oil-soluble N-long chained acyl acidic amino acid mono- and/ordi-ester represented by the general formula (I) described above (group Cester) and

(2) at least one ester selected from the group consisting of mono-and/or di-esters represented by the below-given general formula (II)(group A ester), mono- and/or di-esters represented by the below-givengeneral formula (III) (group B ester) and di-esters represented by thebelow-given general formula (IV) and/or (IVa) (group D ester), andcontaining at least 5 mol% of the group C ester represented by theabove-described general formula (I). ##STR3## where each of X' and Y',which may be identical with or different from each other, represents anester forming residue of a liquid higher alkyl or alkenyl mono-hydricalcohol with 8 to 30 carbon atoms, or one of them is an ester formingresidue of a liquid higher alkyl or alkenyl mono-hydric alcohol with 8to 30 carbon atoms, while the other of them represents H, and n and CORhave respectively the same meanings as those in the general formula (I).##STR4## where each of Xa" and Y", which may be identical with ordifferent from each other, represents an ester forming residue of asolid alkyl mono-hydric alcohol with 12 to 38 carbon atoms, or one of X"and Y" represents an ester forming residue of a solid alkyl mono-hydricalcohol with 12 to 38 carbon atoms, while the other of them representsH, and n and COR have respectively the same meanings as those in thegeneral formula (I). ##STR5## where each of Xa' and Ya', which may beidentical with or different from each other, represents an ester formingresidue of a liquid higher alkyl or alkenyl mono-hydric alcohol with 8to 30 carbon atoms, each of Xa" and Ya", which may be identical with ordifferent from each other, represents an ester forming residue of asolid alkyl mono-hydric alcohol with 12 to 38 carbon atoms, and n andCOR have respectively the same meanings as those in the general formula(I).

The synthesis method for the esters represented by the general formula(I) (group C ester) has already been explained.

The esters represented by the general formula (II) (group A ester) andthe esters represented by the general formula (III) (group B ester) maybe synthesized by known methods.

The mixed di-esters of the alkyl alcohol and the alkenyl alcoholrepresented by the general formulae (IV) and (IVa) (group D ester) mayalso be synthesized by known methods.

It has been found by the present inventors that a remarkable effect canbe obtained by an oily composition comprising a mixture of an esterbelonging to the group C ester and at least one ester selected from thegroup consisting of esters belonging to the group A ester, group B esterand group D ester, in which the ratio of the group C ester in themixture is at least 5 mol%.

The fourth aspect of the present invention resides in perfumingcosmetics comprising the ester of the first aspect or the oilycomposition according to the second or third aspect of the presentinvention.

In a case of incorporating the ester or the oily composition accordingto the present invention into perfuming cosmetics, it can be used byblending as a substitute for an oily substrate, for example, animal andvegetable oils such as squalane, castor oil, bee wax, lanoline, jojobaoil, carnauba wax, tung oil, sesami oil, evening primerose oil, palm oiland minc oil; mineral oils such as solid paraffin, silicone oil,sericin, liquid paraffin or vaseline; synthetic oils such asisopropylmyristate and synthetic polyether; and emollient agents such asstearic acid cholesteryl ester and hydroxystearic acid cholesterylester, or in combination with some of such oily substrates.

The present inventors have found that when the ester or oily compositionas described above is incorporated into skin cosmetics such as facewashing cream, face washing foam, cleansing cream, massage cream, coldcream, moisture cream, milky lotion, cosmetic liquid, pack, men's skincosmetics and baby's skin protector, it can provide particularlyexcellent performance in the functions and in the emulsifying propertyas the oily substrate and can provide an emulsion product with excellentskin affinity, since it contains a sterol ester different from higheralcohol diester of N-long chained acyl acidic amino acid.

At the same time, the following facts have also been found; (i) If someconventional sterol ester other than the sterol ester of N-long chainedacyl acidic amino acid is incorporated into an emulsion product, it hasa drawback of giving heavy feeling of use to the product, whereas anemulsion product having extremely smooth feeling of use can be obtainedin a case of using the ester or the oily composition according to thepresent invention as described above, (ii) The ester and the oilycomposition according to the present invention have no sensitivity andare oleo-phase materials having high safety, (iii) When the ester or theoily composition according to the present invention is incorporated, inparticular, into foundation cosmetics or make-up cosmetics such asfoundation cream, foundation lotion, face powder, lip rouge, lip cream,cheek rouge, eye make-up, eyebrow pencil, eyelash cosmetics, or nailcosmetics, anti-santan cosmetics, perfume or an eau de cologne, it ispossible to provide products with preferred dispersibility of dyes, goodspreadability, high water repellency and not being removed by sweat,(iv) When it is used for a hair caring product such as hair cream,perfumed oil, hair liquid, pomade, stick pomade, liquid hairconditioner, set lotion, treatment, hair tonic, hair spray or haircolor, it can provide hairs with softness and luster, (v) When it isincorporated into aerosol products, a one liquid phase product havinggood compatibility with a spraying agent such as LPG can be prepared,and (vi) When it is added, for example, to shampoo, rinse, soap, bathcosmetics, shaving cosmetics, it can provide shampoo or rinse withstrong hair affinity and conditioning effect, since this is an aminoacid derivative, thereby giving moistened feeling, while it can providesoap, bath cosmetics and having cosmetics an effect of leaving oilcontent after use to protect skins against roughing. The fourth aspectof the present invention is based on such findings.

Surface active agents that can be blended with or incorporated into theperfuming cosmetics is one or a mixture of two or more of surface activeagents selected from the group consisting of various kinds of surfaceactive agents, for example, anionic surface active agents such as N-longchained fatty acid acyl glutamic acid salts, N-long chained fatty acidacyl sarcosine salts, N-long chained fatty acid acyl-N-methyl taurinesalts, N-acyl-N-methyl-β-alanininate alkyl sulfate, alkyl benzenesulfonate, alkyloxy sulfonate, fatty acid amide ether sulfate, fattyacid salts, sulfosuccinic acid higher alcohol ester salts,polyoxyethylene alkyl sulfates, alkyl phosphates, isethionic acid fattyacid esters and alkyl ether carboxylates; nonionic surface activeagents, for example, of an ether type such as glycerine ether andpolyoxyethylene ether thereof, ether ester type such as polyoxyethyleneether of glycerine ester and polyoxyethylene ether of sorbitane ester,ester type such as polyoxyethylene fatty acid esters, glycerine esters,sorbitane esters and sucrose fatty acid esters and nitrogen-containingtype such as fatty acid alkanol amides and polyoxyethylene fatty acidamides; cationic surface active agents, for example, aliphatic aminesalts such as alkyl ammonium chlorides and dialkyl ammonium chlorides,quarternary ammonium salts thereof, aromatic quaternary ammonium saltsuch as benzalconium salt and fatty acid acyl alginic esters; as well asamphoteric surface active agents, for example, of a betaine type such ascarboxy betaine, amino carboxylic acid type, and imidazolinederivatives.

As the aqueous phase ingredient, there can be mentioned polyhydricalcohols such as glycerine, ethylene glycol and 1,3-butylene glycol;water-soluble high polymers such as polyethylene glycol, alginate,carboxymethyl cellulose, hyaluronic acid, water-soluble chitin andsodium polyglutamate; sugar alcohol such as sorbitol and mannitol, andEO or PO addition adducts thereof; organic acids such as citric acid,succinic acid, lactic acid and PCA, and salts thereof, as well as loweralcohols such as ethanol and propanol.

As the powdery ingredient, there can be mentioned inorganic powders suchas talc, kaoline, titanium dioxide and mica sericite, as well as organicpowders such as N-mono-long chained acyl basic amino acids, guanine andlaminate resin pearl.

The perfuming cosmetics according to the present invention can furthercontain customary cosmetic aids, for example, whitening agent,thickening agent, softening agent, moistening agent, fatting agent,moderating agent, wetting agent, preserving agent, UV absorber,chemicals, defoaming agent, chelating agent, protection colloid,perfume, colorant, or optional ingredients ordinarily used forcosmetics.

The amount of the ester or the oily composition according to the presentinvention added to perfuming cosmetics is such an amount that theaddition effect of the ester or the oily composition according to thepresent invention can be attained in each of perfuming cosmetics and itcan be determined easily by those skilled in the art.

The ester mixture according to the present invention can be used also asan oleo-phase starting material for medicines for external application.

EXAMPLE

The present invention will now be explained more specifically referringto preparation examples, blending examples and application examples(preparation examples for perfuming cosmetics).

Preparation Example 1 Synthesis of N-lauroyl-L-glutamic acidmonocholesterol ester (A) (group C ester)

Into a 1000 ml flask, 165 g (0.5 mol) of N-lauroyl-L-glutamic acid and300 ml of toluene were charged and, further, 194 g (0.5 mol) ofcholesterol (manufactured by Riken Vitamine Co.) was added.Subsequently, 0.5 ml of sulfuric acid was added as a catalyst, and themixture was heated to 130°˜140° C. to carry out esterifying reaction forabout 4 hours.

After repeating water washing, toluene was removed by distillation, toobtain 320 g of a waxy product. The product had an acid value of 82.4and a saponification value of 161.3 and it can be seen that the productwas a mono-ester.

Preparation Example 2 Synthesis of N-lauroyl-L-glutamic aciddicholesterol ester (B) (group C ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1 except for using 406 g (1.05 mol) of cholesterol,480 g of an oily product was obtained.

The product had an acid value of 4.52 and a saponification value of105.2 and it can be seen that the product was a di-ester.

Preparation Example 3 Synthesis of N-lauroyl-L-glutamicacid-α-cholesterol, ω-behenyl alcohol di-ester (C) (group Ca ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1 except for using 203 g cholesterol and 169 g ofbehenyl alcohol (manufactured by Kao Corporation), 483 g of a waxyproduct was obtained.

The product had an acid value of 0.48 and a saponification value of117.6 and it can be seen that the product was a di-ester.

Preparation Example 4 Synthesis of N-lauroyl-L-glutamicacid-α-cholesterol, ω-2-octyl dodecanol di-ester (D) (group C ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1 except for using 203 g of cholesterol and 156 g ofoctyl dodecanol (manufactured by Shin-Nippon Rika Co.), 463 g of a waxyproduct was obtained.

The product had an acid value of 3.76 and a saponification value of113.6 and it can be seen that the product was a di-ester.

Preparation Example 5 Synthesis of N-stearoyl-L-glutamicacid-α-cholesterol, ω-behenyl alcohol di-ester (E) (group Ca ester)

In the same procedures as those in the esterifying reaction inPreparation Example 1, 480 g of a waxy product was obtained by using 203g of N-stearoyl-L-glutamic acid instead of N-lauroyl-L-glutamic acid andusing 203 g of cholesterol and 169 g of behenyl alcohol.

The product had an acid value of 2.56 and a saponification value of105.2, and it can be seen that the product was a di-ester.

Preparation Example 6 Synthesis of N-stearoyl-L-glutamicacid-α-cholesterol, ω-2-octyldodecanol di-ester (F) (group C ester)

In the same procedures as those in the esterifying reaction inPreparation Example 1, 495 g of a viscous liquid product was obtained byusing 203 g of N-stearoyl-L-glutamic acid instead ofN-lauroyl-L-glutamic acid and using 203 g of cholesterol and 156 g of2-octyldodecanol.

The product had an acid value of 3.23 and a saponification value of107.5 and it can be seen that the product was a di-ester.

Preparation Example 7 Synthesis of N-lauroyl-L-glutamicacid-α-dihydrocholesterol mono-ester (G) (group C ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, 328 g of a waxy product was obtained by using 204g of dihydrocholesterol instead of cholesterol.

The product had an acid value of 83.4 and a saponification value of1642, and it can be seen that the product was a mono-ester.

Preparation Example 8 Synthesis of N-lauroyl-L-glutamicacid-α-dihydrocholesterol, ω-behenyl alcohol di-ester (H) (group Caester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, 473 g of a soft pasty product was obtained byusing 204 g of dihydrocholesterol and 169 g of behenyl alcohol insteadof cholesterol.

The product had an acid value of 3.11 and a saponification value of111.6 and it can be seen that the product was a di-ester.

Preparation Example 9 Synthesis of N-lauroyl-L-glutamic acid-phytosterolmonoester (I) (group C ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, a product was obtained by using 215 g ofphytosterol (manufactured by Eizai Co.) instead of cholesterol.

The product had an acid value of 80.4 and a saponification value of159.4, and it can be seen that the product was a mono-ester.

Preparation Example 10 Synthesis of N-lauroyl-L-glutamicacid-α-phytosterol, ω-behenyl alcohol diester (H) (group Ca ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, a product was obtained by using 215 g ofphytosterol and 169 g of behenyl alcohol instead of cholesterol.

The product had an acid value of 4.25 and a saponification value of109.4, and it can be seen that the product was a mono-ester.

Preparation Example 11 Synthesis of N-lauroyl-L-glutamicacid-α-dihydrocholesterol, ω-2-octyldodecanol di-ester (K) (group Cester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, 473 g of a pasty product was obtained by using204 g of dihydrocholesterol and 156 g of 2-octyldodecanol instead ofcholesterol.

The product had an acid value of 2.03 and a saponification value of115.3, and it can be seen that the product was a mono-ester.

Preparation Example 12 Synthesis of N-lauroyl-L-glutamicacid-α-phytosterol, ω-2-octyldodecanol di-ester (L) (group C ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, 483 g of a pasty product was obtained by using215 g of phytosterol and 156 g of 2-octyldodecanol instead ofcholesterol.

The pasty product had an acid value of 2.34 and a saponification valueof 112.1, and it can be seen that the product was a mono-ester.

Preparation Example 13 Synthesis of N-lauroyl-L-glutamic acid behenylalcohol mono-ester (M) (group B ester)

Quite in the same procedures as those in the esterifying reaction ofPreparation Example 1, 301 g of a waxy product was obtained by adding169 g of behenyl alcohol instead of cholesterol.

The product had an acid value of 89.57 and a saponification value of179.3, and it can be seen that the product was a mono-ester.

Preparation Example 14 Synthesis of N-lauroyl-L-glutamic acid behenylalcohol di-ester (N) (group B ester)

443.5 g of a waxy product was obtained by using 338 g of behenyl alcoholin the esterifying reaction of Preparation Example 13.

The product had an acid value of 1.28 and a saponification value of 1176, and it can be seen that the product was a di-ester.

Preparation Example 15 Synthesis of N-lauroyl-L-glutamicacid-α-2-octyldodecyl alcohol mono-ester (0) (group A ester)

288 g of a product was obtained by using 156 g of 2-octyldodecanolinstead of behenyl alcohol in the esterifying reaction of PreparationExample 13.

The product had an acid value of 93.23 and a saponification value of184.0, and it is found that the product was a mono-ester.

Preparation Example 16 Synthesis of N-lauroyl-L-glutamicacid-α-2-octyldodecyl alcohol di-ester (P) (group A ester)

406.7 g of a product was obtained by using 313 g of 2-octyldodecylalcohol in the esterifying reaction of Preparation Example 15.

The product had an acid value of 3.57 and a saponification value of127.4, and it is found that the product was a di-ester.

Preparation Example 17 Synthesis of N-lauroyl-L-glutamic acid-α-behenylalcohol, ω-2-octyldodecyl alcohol di-ester (Q) (group D ester)

447 g of a product was obtained by further adding 156 g of2-octyldodecanol in the esterifying reaction of Preparation Example 13.

The product had an acid value of 3.74 and a saponification value of123.8 and it is found that the product was a di-ester.

Preparation Example 18

One mol of N-lauroyl-L-glutamic acid and an alcohol mixture (0.6 mol ofcholesterol, 1 mol of 2-octyldodecyl alcohol and 0.4 mol of behenylalcohol) were charged in a reaction vessel, to which 200 ml of toluenewas added as a solvent. Then, the reaction mixture was stirred underheating, to which 1 mol of H₂ SO₄ was added as a catalyst, and the masswas brought into reaction by continuing stirring and heating at 90°˜140°C. for about 4 hours. Meanwhile, the by-produced water was sufficientlyremoved.

After the completion of the reaction, the reaction mixture wasneutralized with an aqueous solution of potassium hydroxide and thesolvent toluene was recovered to obtain an aimed-at mixture of threekinds of esters (specimen No. 19).

Yield=98.2%, acid value=3.06, saponification value=121.87, pH (1%)=5.55,the molar ratio of the group A ester, group B ester and group C ester(%)=0:20:30.

Preparation Example 19

One mol of N-lauroyl-L-glutamic acid and an alcohol mixture (0.6 mol ofphytosterol, 1.2 mol of 2-octyldodecyl alcohol and 0.2 mol of behenylalcohol) were charged in a reaction vessel and the content was meltedunder stirring and heating. Then, 1 ml of H₂ SO₄ was added as a catalystand the mass was brought into reaction under a nitrogen atmosphere bycontinuing stirring and heating at 100°˜140° C. for about 5 hours.

After the completion of the reaction, the reaction mixture wasneutralized with an aqueous solution of potassium hydroxide to obtain anaimed-at mixture of three kinds of esters (specimen No. 20).

Yield=98.0%, acid value=4.25, saponification value=106.23, pH (1%)=5.58,the molar ratio of the group A ester, group B ester and group C ester(%)=60:10:30.

Preparation Example 20

One mol of N-lauroyl-L-glutamic acid and an alcohol mixture (0.5 mol ofcholesterol and 1.5 mol of 2-octyldodecyl alcohol) were charged in areaction vessel, to which 200 ml of toluene was added as a solvent, towhich 0.05 mol of p-toluene sulfonic acid was added as a catalyst, andthe mixture was brought into reaction by continuing stirring and heatingat 90°˜140° C. for about 4 hours. Meanwhile, the by-produced water wassufficiently removed.

After the completion of the reaction, the reaction mixture wasneutralized with an aqueous solution of sodium hydroxide and the solventtoluene was recovered to obtain an aimed-at mixture of three kinds ofesters (specimen No. 21).

Yield=98.0%, acid value=1.48, saponification value=121.36, pH (1%)=5.69,the molar ratio of the group A ester, group B ester and group C ester(%)=15:0:25.

Blending Examples 1˜21

The compounds A˜Q obtained in Preparation Examples 1˜17 were mixed inthe ratios shown in Table 2 to obtain blended compositions of specimensNos. 1˜18. The mixtures obtained in Preparation Example 18˜20 areindicated as specimens Nos. 19˜21 the same table.

The compositions and physical properties of the specimens are also shownin Tables 2˜4.

                                      TABLE 2                                     __________________________________________________________________________    Composition of alcohol and kind of acyl group of each specimen                       Composition ratio (mol %)                                                     Liquid                                                                 Spe-   higher                                                                              Solid                                                            ci-    alkyl or                                                                            higher                                                           men    alkenyl                                                                             alkyl      Acyl Mixing ratio of compounds                        No.    alcohol                                                                             alcohol                                                                            Sterol                                                                              group                                                                              A B C D E F G H I J K L M N O P Q                __________________________________________________________________________    Exam-                                                                              1 2-Octyldo-                                                                          --   Cholesterol                                                                         Lauroyl                                                                              1   3                       1                  ples   decanol                                                                       50:50                                                                       2 2-Octyldo-                                                                          --   Cholesterol                                                                         Lauroyl    5                       5                         decanol                                                                       75:25                                                                       3 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl  4 2                       4                         decanol                                                                             alcohol                                                                 50:20:30                                                                    4 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl                                                                            1   4 2                 1   2 2                         decanol                                                                             alcohol                                                                 40:25:35                                                                    5 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl                                                                            1   2                       5 5                         decanol                                                                             alcohol                                                                 75:10:15                                                                    6   2-Octyldo-                                                                        Behenyl                                                                            Cholesterol                                                                         Lauroyl  1                         1 3                       decanol*                                                                            alcohol                                                                 50:40:10                                                                    7 2-Octyldo-                                                                          --   Cholesterol                                                                         Stearoyl       1                                             decanol                                                                       50:50                                                                       8 2-Octyldo-                                                                          Behenyl                                                                            Phytosterol                                                                         Lauroyl                2   1       2                         decanol                                                                             alcohol                                                                 50:20:30                                                                    9 2-Octyldo-                                                                          Behenyl                                                                            Dihydro-                                                                            Lauroyl            2     1       2                           decanol                                                                             alcohol                                                                            cholesterol                                                        50:20:30                                                                   10 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Stearoyl     1 2                 1 1                         decanol                                                                             alcohol                                                                 60:10:30                                                                   11 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl  2                   3   1   2                       decanol*                                                                            alcohol                                                                 25:55:20                                                                   12 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl                                                                            1   3 1                 1   1                           decanol                                                                             alcohol                                                                 15:35:50                                                                   13 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl                                                                              2 1 2                                                 decanol                                                                             alcohol                                                                 20:10:70                                                                   14 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl  1 2                       2                         decanol                                                                             alcohol                                                                 60:10:30                                                                   15 --    --   Cholesterol                                                                         Lauroyl                                                                              1                                                     0:0:100                                                                Com-                                                                              16 2-Octyldo-                                                                          Behenyl    Lauroyl                              1                para-  decanol*                                                                            alcohol                                                          tive   50:50:0                                                                Exam-                                                                             17 --    Behenyl                                                                            --    Lauroyl                        1                      ples         alcohol                                                                 0:100:0                                                                    18 2-Octyldo-                                                                          --   --    Lauroyl                            1                         decanol                                                                       100:0:0                                                                Exam-                                                                             19 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Lauroyl                                               ples   decanol                                                                             alcohol                                                                 50:20:30                                                                   20 2-Octyldo-                                                                          Behenyl                                                                            Cholesterol                                                                         Stearoyl                                                     decanol                                                                             alcohol                                                                 60:10:30                                                                   21 2-Octyldo-                                                                          --   Cholesterol                                                                         Lauroyl                                                      decanol                                                                       75:0:25                                                                __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                        Physical property and nature of amino acid type sterol ester                                    Saponi-                                                     Specimen  Acid    fication                                                    No.       value   value     Nature                                            ______________________________________                                         1        3.76    113.59    Viscous clouded liquid                             2        1.48    121.36    Viscous clear liquid                               3        3.06    121.87    Soft clouded paste                                 4        2.38    118.84    Soft wax                                           5        2.42    122.51    Soft clouded paste                                 6        1.37    124.35    Soft wax                                           7        3.20    108.98    Viscous clouded liquid                             8        3.34    119.41    Soft paste                                         9        2.83    120.39    Soft paste                                        10        1.25    106.23    Soft paste                                        11        3.42    115.71    Wax                                               12        3.12    111.53    Wax                                               13        2.83    112.03    Viscous paste                                     14        2.68    105.49    Soft clouded paste                                15        4.52    105.21    Wax                                               16        3.74    123.78    Wax                                               17        1.28    117.63    Wax                                               18        3.57    127.40    Liquid                                            19        3.06    121.87    Soft paste                                        20        4.25    106.23    Soft paste                                        21        1.48    121.36    Viscous liquid                                    ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Solubility of amino acid type sterol ester (2%, 30° C.)                               Propy-                                                         Specimen       lene           Olive Castor                                                                              Liquid                              No.    Water   glycol  Ethanol                                                                              oil   oil   paraffin                            ______________________________________                                         1     I       I       S      S     S     S                                    2     I       I       S      S     S     S                                    3     I       I       S      S     S     S                                    4     I       I       S      S     S     S                                    5     I       I       S      S     S     S                                    6     I       I       S      S     S     S                                    7     I       I       S      S     S     S                                    8     I       I       S      S     S     S                                    9     I       I       S      S     S     S                                   10     I       I       S      S     S     S                                   11     I       I       S      S     S     S                                   12     I       I       S      S     S     S                                   13     I       I       S      S     S     S                                   14     I       I       S      S     S     S                                   15     I       I       S      S     S     S                                   16     I       I       S      S     S     S                                   17     I       I       S      S     S     S                                   18     I       I       S      S     S     S                                   19     I       I       S      S     S     S                                   20     I       I       S      S     S     S                                   21     I       I       S      S     S     S                                   ______________________________________                                         I: insoluble                                                                  S: soluble                                                               

Application examples will be shown below in which the blending ratio ofthe ingredients is based on the weight percentage.

Application Example 1 (O/W type cream)

The following ingredient (1) was warmed to 80° C. while the ingredient(2) was warmed to 50° C., and the ingredient (2) was gradually added tothe ingredient (1) under stirring to emulsify. The ingredient (3) wasadded at 50° C. under stirring and water cooling and then cooled to 35°C. to prepare a product (Product A).

    ______________________________________                                        Ingredient (1)                                                                Squalane               8.0                                                    Cetyl octanate         13.0                                                   Ester mixture of the invention                                                                       10.0                                                   (Specimen No. 5)                                                              Hardened oil           5.0                                                    Behenyl alcohol        1.0                                                    Stearic acid           2.0                                                    Self-emulsifiable glycerine monostearate                                                             4.0                                                    Diglycerine oleate     1.0                                                    Dimethyl polysiloxane  0.3                                                    Ingredient (2)                                                                Preservative           0.2                                                    Sodium N-stearoyl-L-glutamate                                                                        0.4                                                    Xanthane gum            0.05                                                  1,3-butylene glycol    7.0                                                    Purified water         47.85                                                  Ingredient (3)                                                                Perfume                 0.22                                                                         100.0%                                                 ______________________________________                                    

An O/W type cream with luster of opaque color and having excellentemollient property and good feeling of use was obtained by blending theester mixture according to the present invention (specimen No. 3).

Then, a comparative product (Product B) was prepared by usingN-lauroyl-L-glutamic acid dioctyl dodecyl ester (Specimen No. 18)instead of the ester mixture of the present invention (Specimen No. 3)in the ingredients of Product A.

Then, a blind functional test was conducted using a panel of 40 adultsof 18˜26 years (20 men and 20 women).

The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Test items                                                                    Spreadability  Emollient property                                                                          Feeling of use                                   Product                                                                              Man    Woman    Man    Woman  Man  Woman                               ______________________________________                                        A      17     18       18     20     17   19                                  B       3      2        2      0      3    1                                  ______________________________________                                         *Numerical values in the table show the number of persons who judged best                                                                              

Between products A and B, satisfactory results were obtained for ProductA with respect to all of the test items.

Further, the results of the test for the aging change of Product A and Bare shown in Table 6.

                  TABLE 6                                                         ______________________________________                                               Number of days elapsed                                                 Product  4 days  7 days      30 days                                                                             60 days                                    ______________________________________                                        A        ◯                                                                         ◯                                                                             ◯                                                                       ◯                              B        ◯                                                                         Δ     Δ                                                                             X                                          ______________________________________                                         ◯: Stable emulsion,                                               Δ: Slight segregation observed,                                         X: Segregation and denaturation observed.                                     Emulsion stability (cycles of 40° C. (48 hr) ⃡             0° C. (48 hr))                                                    

From the results, Product A shows satisfactory stability, whereasProduct B is unsatisfactory.

As can be seen from the various tests described above, the ester mixtureaccording to the present invention when incorporated into a cream canimprove the cream in the performance such as spreadability, emollientproperty and feeling of use and, in addition, since it has excellenthydrating property and self-emulsifiability, the aging stability ofproducts can also be improved.

An emollient cream quite in the same composition as in Product A exceptfor blending Specimen No. 19 instead of Specimen No. 3 was prepared andthe results obtained were substantially identical.

Application Example 2 (W/O type foundation cream)

The following ingredient (1) was warmed to 85° C. (The metallic soapshad been dissolved by heating to 90°˜95° C.), while the followingingredient (2) was warmed to 85° C. The ingredient (2) was graduallyadded to the ingredient (1) under stirring to emulsify. The ingredient(3) was added at 50° C. under cooling and stirring and then cooled to35° C., to obtain a foundation cream (Product C).

    ______________________________________                                        Ingredient (1)                                                                Squalane                   15.0                                               Sericin                    3.0                                                Bee wax                    1.0                                                Jojoba oil                 3.0                                                Ester mixture of the invention (Specimen No. 8)                                                          4.0                                                Polyglycerine di-isostearate                                                                             6.0                                                Magnesium myristate        1.0                                                Aluminum stearate          0.5                                                Pigment                    15.0                                               Ingredient (2)                                                                Preservative               0.2                                                Magnesium sulfate          0.1                                                Sorbitol                   5.0                                                Sodium hyaluronate (1% aqueous solution)                                                                 2.0                                                Purified water             44.0                                               Ingredient (3)                                                                Perfume                    0.2                                                                           100.0%                                             ______________________________________                                    

As for the perfuming cosmetics of the present invention (Product C),since the ester mixture of the present invention (Specimen No. 8) is astrongly hydrating oil-soluble material, a W/O emulsion of excellentstability can be attained by blending the ester mixture. Further, theester mixture of the present invention shows good dispersibility fortitanium, talc or the like and can provide a W/O foundation cream ofexcellent skin affinity and depositability when the ester mixture inadded.

Application Example 3 (milky lotion)

The following ingredient (1) was warmed to 85° C. and it was graduallyadded to the following ingredient (2) under stirring and then thefollowing ingredient (3) was added. They were stirred under watercooling to obtain a milky lotion at 30° C. (Product D).

    ______________________________________                                        ingredient (1)                                                                Squalane                   10.0                                               Ester mixture of the invention (Specimen No. 5)                                                          3.0                                                Isocetyl octanate          9.0                                                Glycerine trioctanate      4.0                                                Propylene glycol stearate  0.5                                                Behenyl alcohol            0.5                                                Stearic acid               1.0                                                Oleophilic glycerine monostearate                                                                        1.0                                                Diglycerine oleate         0.5                                                Polyethylene glycol stearate                                                                             2.5                                                Ingredient (2)                                                                Preservative               0.2                                                Carboxyvinyl polymer (1.0% aqueous solution)                                                             15.0                                               Oleyl phosphoric acid      0.4                                                1,3-butylene glycol        5.0                                                Purified water             46.9                                               Ingredient (3)                                                                L-arginine                 0.3                                                Purified water             0.2                                                                           100.0%                                             ______________________________________                                    

When the ester mixture of the invention (Specimen No. 5) wasincorporated, an emulsion with fine emulsified particles and ofexcellent aging stability could obtained, and the skin affinity anddepositability could can be improved by incorporating the ester mixtureof the invention, to obtain an emulsion with good feeling of use.

Application Example 4 (Hair lotion)

The following ingredient (1) was warmed to 80° C. and the followingingredient (2) was warmed to 85° C. The ingredient (2) was graduallyadded to the ingredient (1) under stirring. The ingredient (3) was addedto 50° C. while stirring under cooling and then the mixture was cooledto 35° C. to obtain a hair lotion (Product E).

    ______________________________________                                        Ingredient (1)                                                                Liquid paraffin            15.0                                               Vaseline                   5.0                                                Isopropyl myristate        10.0                                               Bee wax                    1.0                                                Ester mixture of the invention (Specimen No. 1)                                                          10.0                                               Stearic acid               1.0                                                Propylene glycol stearate  1.0                                                Polyglycerine oleate       4.0                                                Hydrogenated soy-bean lecithin                                                                           1.0                                                Ingredient (2)                                                                Preservative               0.2                                                Sodium N-stearoyl-L-glutamate                                                                            0.4                                                Xanthane gum (1.0% aqueous solution)                                                                     10.0                                               1,3-butylene glycol        5.0                                                Purified water             36.1                                               Ingredient (3)                                                                Perfume                    0.3                                                                           100.0%                                             ______________________________________                                    

Since the ester mixture of the invention (Specimen No. 1) is a startingmaterial having high compatibility with other starting materials such ashydrocarbon, wax and lecithin and having excellent emulsifyingperformance, products of high commercial value can be obtained. Inaddition, since the ester mixture of the invention has excellentperformance such as affinity, depositability and moisture keepingproperty, hair cosmetics of high commercial value can be obtained.

Application Example 5 (Hair rinse)

The following ingredient (1) was warmed to 85° C. and the ingredient (2)was warmed to 80° C. The ingredient (1) was gradually added to theingredient (2) under stirring. Then, the ingredient (3) was added at 50°C. while stirring under cooling, to obtain a hair rinse at 35° C.(Product F).

    ______________________________________                                        Ingredient (1)                                                                Liquid paraffin           2.0                                                 Ester mixture of the invention (Specimen No. 10)                                                        2.0                                                 Cetostearyl alcohol       4.0                                                 Polyglycerine oleate      1.0                                                 Alkyltrimethyl ammonium chloride                                                                        3.0                                                 Polyoxyethylene glycerine pyroglutamate                                                                 0.5                                                 isostearate                                                                   Ingredient (2)                                                                Preservative              0.1                                                 1,3-butylene glycol       8.0                                                 Purified water            79.1                                                Ingredient (3)                                                                Perfume                   0.3                                                                           100.0%                                              ______________________________________                                    

The ester mixture (Specimen No. 10) of the invention forms a complexcompound together with a cationic surface active agent, higher alcoholor the like to increase the rinsing and conditioning effects, has goodcompatibility, for example, with cetanol and stearyl alcohol to be acrystallization inhibitor for high melting point materials at lowtemperatures.

Application Example 6 (Hair treatment cream)

The following ingredient (1) was warmed to 80° C., while the ingredient(2) was warmed to 85° C. The ingredient (2) was gradually added to theingredient (1) under stirring. Then, the ingredient (3) was added at 50°C. while stirring under cooling, to obtain a product at 35° C. (ProductG).

    ______________________________________                                        Ingredient (1)                                                                Liquid paraffin            9.0                                                Cetyl octanate             4.0                                                Ester mixture of the invention (Specimen No. 7)                                                          4.0                                                Cetostearyl alcohol        5.0                                                Propylene glycol stearate  2.0                                                Glycerine stearate         1.0                                                Polyethylene glycol stearate                                                                             1.0                                                Distearyldimethyl ammonium chloride                                                                      1.0                                                Ingredient (2)                                                                N-cocoyl-arginine-ethyl pyrrolidone carboxylate                                                          0.5                                                1,3-butylene glycol        5.0                                                Chitin (1.0% aqueous solution)                                                                           10.0                                               Purified water             57.2                                               Ingredient (3)                                                                Perfume                    0.3                                                                           100.0%                                             ______________________________________                                    

Since the ester mixture (Specimen No. 7) of the invention has goodcombatibility with oleo-phase starting material, for example, cationicsurface active agent and higher alcohol and it also has excellentemulsifying performance, products in a good emulsified state and highlyopaque nature can be obtained. In addition, since this is an amino typematerial, it can provide an excellent protecting effect for damagedhairs when used in combination with an amino acid type cationic surfaceactive agent.

Then, a comparative product (Product H) was prepared by blendingdi-POE(2 mol)-stearyl ether N-lauroyl glutamate instead of the estermixture of the mixture (Specimen No. 7) in the ingredients of Product G(product of the invention) and a functional test was conducted.

The results are shown in the following Table 7.

                  TABLE 7                                                         ______________________________________                                               Spread-                                                                       ability  Combing  Smooth-                                                                              Moistened                                     Product                                                                              upon use property ness   feeling Luster                                ______________________________________                                        G      ◯                                                                          ◯                                                                          ◯                                                                        ◯                                                                         ◯                         H      Δ  Δ  ◯                                                                        Δ X                                     ______________________________________                                         ◯: particularly preferred                                         Δ: ordinary                                                             ◯: preferred                                                      X: poor                                                                  

As apparent from Table 7, Product G provided good results with respectto all of the test items as compared with Product H.

Application Example 7 (Hair shampoo)

The following ingredients (1) and (2) were warmed to 80° C. and 85° C.,respectively. The ingredient (2) was gradually added to the ingredient(1) while stirring. Then, the mixture was cooled and the ingredient (3)was added at 50° C. and the resultant mixture was cooled to 30° C., toobtain a shampoo (Product I).

    ______________________________________                                        Ingredient (1)                                                                Triethanolamine N-cocoyl-L-glutamate                                                                    20.0                                                (30% aqueous solution)                                                        Sodium lauroyl methyl-β-alanine                                                                    20.0                                                (30% aqueous solution)                                                        Coconut oil fatty acid amide propyl betaine                                                             30.0                                                (30% aqueous solution)                                                        Cationized cellulose      0.5                                                 Propylene glycol          5.0                                                 Preservative              0.2                                                 Purified water            13.0                                                Ingredient (2)                                                                Coconut oil fatty acid diethanolamide                                                                   4.0                                                 Polyoxyethylene glycerine triisostearate                                                                3.0                                                 Propylene glycol laurate  2.0                                                 Ester mixture of the invention (Specimen No. 14)                                                        2.0                                                 Ingredient (3)                                                                Perfume                   0.3                                                                           100.0%                                              ______________________________________                                    

Since the ester mixture of the invention (Specimen No. 14) is an aminoacid type derivative, it can give a shampoo having high hair affinityand depositability and a conditioning effect.

Application Example 8 (Cleansing foam)

The following ingredients (1) and (2) were warmed to 85° C. and 80° C.,respectively. The ingredient (1) was gradually added to the ingredient(2) while stirring. Then, the ingredient (3) was added to 50° C. whilecooling the mixture and the resultant mixture was further cooled to 35°C. to obtain a product (Product J).

    ______________________________________                                        Ingredient (1)                                                                Ester mixture of the invention (Specimen No. 9)                                                          4.0                                                Lauric acid                3.0                                                Myristic acid              3.0                                                Polyoxyethylene hardened caster oil                                                                      2.0                                                Coconut oil fatty acid diethanolamine                                                                    8.0                                                Ingredient (2)                                                                Sodium hydroxide           0.8                                                Polyethylene glycol        15.0                                               Propylene glycol           15.0                                               Sodium N-lauroyl-L-glutamate                                                                             30.0                                               Purified water             19.0                                               Ingredient (3)                                                                Perfume                    0.2                                                                           100.0%                                             ______________________________________                                    

When the ester mixture of the invention (Specimen No. 9) is used as anon-polar material for soap and cleansing foam of sodium N-acylL-glutamate, it can prevent cracking of the soap and improve thecreaminess of the cleansing cream. In addition, it can provide soap orcleansing foam products with excellent performance as a super fattingagent and an emollient agent.

Application Example 9 (Lip stick (1))

The following ingredient (1) was dissolved under heating substantiallyat 80° C and then mixed uniformly. The ingredient (2) was added, and themixture was kneaded with a roll mill and uniformly dispersed. Then, themixture was melted again, the ingredient (3) was added and, afterdefoaming, the resultant mixture was cast into a molding dye andsolidified by quenching, to obtain a lip stick (1).

    ______________________________________                                        Ingredient (1)                                                                Castor oil                51.9                                                Octyl dodecanol           15.0                                                Ester mixture of the invention (Specimen No. 19)                                                        5.0                                                 Liquid lanoline           5.0                                                 Bee wax                   4.0                                                 Ozokerite                 5.0                                                 Candelilla wax            7.0                                                 Carnauba wax              2.0                                                 Ingredient (2)                                                                Titanium oxide            1.0                                                 Red No. 201               1.0                                                 Red No. 202               2.0                                                 Yellow No. 4 aluminum lake                                                                              1.0                                                 Red No. 223               0.1                                                 Ingredient (3)                                                                Perfume                   appropriate                                                                   amount                                              Antioxidant               appropriate                                                                   amount                                              Preservative              appropriate                                                                   amount                                                                        100.0%                                              ______________________________________                                    

The resultant lip stick (1) was stable for a long period of time with nosweating. In addition, it had clear color and appropriate strength.Further, it had good affinity with skin and excellent spreadability.

Application Example 10 (Lip stick (2))

A lip stick (2) was obtained in the same way as in the lip stick (1) byusing the following ingredients (1), (2) and (3).

    ______________________________________                                        Ingredient (1)                                                                Ozokerite                5.0                                                  Sericin                  5.0                                                  Solid paraffin           10.0                                                 Ester mixture of the invention (Specimen No. 2)                                                        40.0                                                 Glycerine trioctanate    20.0                                                 Octyldodecyl myristate   10.0                                                 Ingredient (2)                                                                Titanium oxide           1.0                                                  Red No. 201              1.0                                                  Red No. 202              1.0                                                  Blue No. 1 aluminum lake 0.5                                                  Mica titanium            6.5                                                  Ingredient (3)                                                                Perfume                  appropriate                                                                   amount                                               Antioxidant              appropriate                                                                   amount                                               Preservative             appropriate                                                                   amount                                                                        100.0%                                               ______________________________________                                    

The resultant lip stick (2) got the same evaluation as in the lip stick(1).

Application Example 11 (Lip stick (3))

A lip stick (3) was prepared by using the following ingredients. Thatis, after mixing the oily substrates and then melting them underheating, the colorants previously mixed with castor oil and dissolvedand dispersed homogeneously was admixed, to which the perfume and theantioxidant were added, and they were further mixed homogeneously understirring. The liquid was cast into a molding die and rapidly cooled toobtain a lip stick (3).

    ______________________________________                                        Bee wax                   10.0                                                Sericin                   24.0                                                Carnauba wax              8.0                                                 Ester mixture of the invention (Specimen No. 15)                                                        10.0                                                Liquid paraffin           22.0                                                Castor oil                21.0                                                Eosinic acid              2.5                                                 Pigment                   1.0                                                 Perfume                   1.5                                                 Antioxidant               appropriate                                                                   amount                                                                        100.0%                                              ______________________________________                                    

The evaluation result for the resultant lip stick (3) was excellent likethat as for the lip stick (1).

Application Example 12 (Powder foundation (1))

The following ingredient (1) was mixed and pulverized through apulverizer. It was transferred to a high speed blender, mixed with theingredients (2) and (3) and then added to a pigment and uniformly mixed.The mixture was treated by a pulverizer, conditioned for the grain sizeby passing through a sieve and then, compression molded to obtain apowder foundation (1).

    ______________________________________                                        Ingredient (1)                                                                Red iron oxide            3.0                                                 Yellow iron oxide         2.5                                                 Black iron oxide          0.5                                                 Nylon powder              10.0                                                Titanium oxide            10.0                                                Mica                      20.0                                                Talc                      44.0                                                Ingredient (2)                                                                Liquid paraffin           5.0                                                 Octyl dodecyl myristate   2.5                                                 Ester mixture of the invention (Specimen No. 19)                                                        2.5                                                 Ingredient (3)                                                                Preservative              appropriate                                                                   amount                                              Perfume                   appropriate                                                                   amount                                                                        100.0%                                              ______________________________________                                    

The resultant powder foundation (1) well fit with skin and was excellentin spreadability.

Application Example 13 (Powder foundation (2))

In the same procedures as those for the powder foundation (1), thefollowing ingredients (1) and (2) were prepared respectively andcompression molded to obtain a powder foundation (2).

    ______________________________________                                        Ingredient (1)                                                                Titanium oxide           9.0                                                  Zinc oxide               9.0                                                  Kaoline                  47.0                                                 Talc                     20.0                                                 Yellow iron oxide        appropriate                                                                   amount                                               Red iron oxide           appropriate                                                                   amount                                               Ingredient (2)                                                                Surface active agent (sorbitane monooleate)                                                            5.0                                                  Ester mixture of the invention (Specimen No. 3)                                                        6.0                                                  1,3-butylene glycol      4.0                                                  Perfume                  appropriate                                                                   amount                                                                        100.0%                                               ______________________________________                                    

The resultant powder foundation (2) got the same evaluation like that ofthe powder foundation (1) and it was excellent in spreadability.

Application Example 14 (Liquid foundation (1))

The following ingredients (1), (2) and (3) were mixed respectively underheating at 80° C. That is, the ingredient (2) was added to theingredient (1), and then the ingredient (3) was added. Further, theingredient (4) was added, gradually cooled to 40° C., and stirred for 5min in a homomixer, to obtain a liquid foundation (1).

    ______________________________________                                        Ingredient (1)                                                                Stearate acid             3.0                                                 Isopropyl myristate       9.0                                                 Liquid paraffin           1.5                                                 Cetanol                   1.0                                                 Preservative              appropriate                                                                   amount                                              Coloring pigment          8.0                                                 Ester mixture of the invention (Specimen No. 21)                                                        2.0                                                 Ingredient (2)                                                                Triethanolamine           1.5                                                 Water                     25.0                                                Ingredient (3)                                                                Propylene glycol          5.0                                                 Preservative              appropriate                                                                   amount                                              Water                     29.0                                                Ingredient (4)                                                                Bentonite (1% aqueous solution)                                                                         15.0                                                                          100.0%                                              ______________________________________                                    

As the evaluation result of the resultant liquid foundation (1), it wasfound to be a liquid foundation having fresh feeling of use and giving amoistening effect to skin.

Application Example 15 (Liquid foundation (2))

The following ingredient (3) was thoroughly mixed and pulverized bypassing through a pulverizer. As for the ingredient (2), purified waterwas heated to 70° C., and bentonite was added and thoroughly swollen, towhich sodium carboxymethyl cellulose previously dispersed in propyleneglycol was added and dissolved. Triethanolamine and methyl p-oxybenzoatewere added and dissolved. The ingredient (1) was mixed and melted underheating at 70°˜80° C. The thus processed ingredient (3) was added understirring to the thus processed ingredient (2). Subsequently, the mixturewas passed through a colloid mill, heated again at 75° C. and then addedto the ingredient (1) at 80° C. under stirring and then cooled. Then,the ingredient (4) was added at 45° C. and continuously stirred undercooling to room temperature, to obtain a liquid foundation (2).

    ______________________________________                                        Ingredient (1)                                                                Stearic acid             2.4                                                  Propylene glycol monostearate                                                                          2.0                                                  Cetostearyl alcohol      0.2                                                  Ester mixture of the invention (Specimen No. 3)                                                        2.0                                                  Liquid paraffin          3.0                                                  Isopropyl myristate      8.5                                                  Propyl p-oxybenzoate     appropriate                                                                   amount                                               Ingredient (2)                                                                Water                    64.1                                                 Sodium carboxymethyl cellulose                                                                         0.2                                                  Bentonite                0.5                                                  Propylene glycol         4.0                                                  Triethanolamine          1.1                                                  Methyl p-oxybenzoate     appropriate                                                                   amount                                               Ingredient (3)                                                                Titanium oxide           8.0                                                  Talc                     4.0                                                  Coloring pigment         appropriate                                                                   amount                                               Ingredient (4)                                                                Perfume                  appropriate                                                                   amount                                                                        100.0%                                               ______________________________________                                    

The evaluation result for the obtained liquid foundation (2) wasexcellent like that for the liquid foundation (1).

Application Example 16 (Hair mousse)

The following ingredients (1) and (2) were dissolved by warming to 45°C., respectively. The ingredient (1) was added to the ingredient (2)under stirring. The mixture was stirred under cooling, to which theingredient (3) was added at 40° C. and, after cooling to roomtemperature, the resultant base was transferred to an aerosol vessel andthe ingredient (4) was further charged to produce a product.

    ______________________________________                                        Ingredient (1)                                                                Liquid paraffin           2.5                                                 Ester mixture of the invention (Specimen No. 19)                                                        2.0                                                 Polyoxyethylene lauryl ether                                                                            1.0                                                 Ethyl alcohol             15.0                                                Ingredient (2)                                                                Glycerine                 10.0                                                Propylene glycol          1.0                                                 Water-soluble polymer     2.0                                                 Water                     51.2                                                Ingredient (3)                                                                Perfume                   0.3                                                 Ingredient (4)                                                                Propellant (LPG gas)      15.0                                                                          100.0%                                              ______________________________________                                    

Foaming performance of hair mousse products can be improved by blendingthe ester mixture of the present invention. Products having excellenthair affinity and emollient property can be obtained.

What is claimed is:
 1. An oil-soluble N-long chained acyl acidic aminoacid mono- or di-ester represented by the following general formula (I):##STR6## where each of X and Y, which may be identical with or differentfrom each other, represents an ester forming residue of cholesterol ordihydrocholesterol, or one of X and Y represents an ester formingresidue of cholesterol or dihydrocholesterol and the other of themrepresents H, an ester forming residue of a liquid higher alkyl oralkenyl mono-hydric alcohol with 8 to 30 carbon atoms or a solid higheralkyl mono-hydric alcohol with 12 to 38 carbon atoms, COR represents along chained acyl group with 8 to 22 carbon atoms and n is 1 or 2.